CN102311616A - Carbon-fiber-reinforced polyester composite material and preparation method thereof - Google Patents

Carbon-fiber-reinforced polyester composite material and preparation method thereof Download PDF

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Publication number
CN102311616A
CN102311616A CN201010614830A CN201010614830A CN102311616A CN 102311616 A CN102311616 A CN 102311616A CN 201010614830 A CN201010614830 A CN 201010614830A CN 201010614830 A CN201010614830 A CN 201010614830A CN 102311616 A CN102311616 A CN 102311616A
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temperature
district
carbon fiber
thomel
reinforced polyester
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CN102311616B (en
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徐东
徐永
杨海灵
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Polymer Science Shenzhen New Materials Co Ltd
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Polymer Science Shenzhen New Materials Co Ltd
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    • B29C47/92

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  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

The invention discloses a carbon-fiber-reinforced polyester composite material and a preparation method thereof. The composite material comprises the following components by weight percent (%): 60-80% of polyester, 0.1-0.3% of lubricating agent, 0.1-0.3% of antioxidant and 20-40% of carbon fiber. In the invention, surface treatment is carried out on the carbon fiber by virtue of liquid polyacrylonitrile so that the bonding performance between the carbon fiber and a polar polyester resin matrix is improved and mechanical properties of a material are enhanced. The invention has the advantages that: the surface polarity of the carbon fiber is improved; the bonding force between the carbon fiber and the resin matrix is improved; and the obtained carbon-fiber-reinforced polyester material has high strength, high toughness and simple production process and can be widely applied to a high-performance structural material for automobiles, military appliance and aviation.

Description

A kind of carbon fiber reinforced polyester matrix material and preparation method thereof
Technical field
The present invention relates to technical field of macromolecules, relate in particular to a kind of carbon fiber reinforced polyester matrix material and preparation method thereof.
Background technology
Polyester, by polyvalent alcohol and polyprotonic acid polycondensation and the polymkeric substance general name.Mainly refer to polyethyleneterephthalate (PET) and polybutylene terephthalate line style thermoplastic resins such as (PBT).Have HMP, H.T., outstanding resistance toheat and electric durability ability are one type of excellent performance, broad-spectrum engineering plastics.
Thomel has HS, low density, high-temperature resistant, characteristics such as water-fast, corrosion-resistant, is a kind of HS strongthener of excellence.With the carbon fiber reinforced macromolecule resin is that the high performance structures material is used in crucial military project apparatus, aviation.Strengthening the resin major part is polar resin, like polyester, polymeric amide, polyimide etc.Carbon fiber surface polarity very a little less than, very little with the cohesive force of polar resin, therefore generally need carry out just being used for reinforced composite after the surface treatment to it.The polyester composite of thomel enhancing modified has very high specific tenacity, is a kind of structured material of advantage, uses more at automobile, aviation field.
Surface treatment of carbon fibers agent commonly used comprises compositions such as silane coupling agent and vinylformic acid, polyurethanes membrane-forming agent.Silane coupling agent in use is easy to become siloxane oligomer from polycondensation, and actual utilization ratio is low, and with that part of also very easily hydrolysis of the effective chemically bonded of fiberglass surfacing.
Summary of the invention
The technical problem that the present invention will solve provides a kind of carbon fiber reinforced polyester matrix material and preparation method thereof.
For solving the problems of the technologies described above, the present invention adopts following technical scheme: a kind of carbon fiber reinforced polyester matrix material, and it forms by the quality proportioning is (%):
Polyester 60-80%
Lubricant 0.1-0.3%;
Oxidation inhibitor 0.1-0.3%;
Thomel 20-40%.
Wherein, said polyester is polybutylene terephthalate or polyethyleneterephthalate one or both mixtures wherein.
Wherein, said lubricant is a Zinic stearas.
Wherein, said oxidation inhibitor is four [β-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester.
Wherein, said thomel is through liquid polyacrylonitrile surface treatment.
Wherein, said thomel preparation method comprises:
Step 1: with stirring after polyacrylonitrile and the solvent;
Step 2: the solvent that thomel is soaked into step 1;
Step 3: will in 50-300 degree centigrade of baking oven, obtain the polyacrylonitrile surface processed carbon fiber in preoxidation 0.01-100 hour through thomel that soak into to handle.
A kind of composite material and preparation method thereof of carbon fiber reinforced polyester as stated comprises step:
A: by mass percentage resin, lubricant, oxidation inhibitor were mixed in high-speed mixer 4 minutes;
B: each component that mixes places twin screw extruder, presses mass ratio thomel is added extruding pelletization in the forcing machine with the side feeding manner, through the melting mixing extruding pelletization;
C: its processing temperature is district's temperature a: 210-220 ℃, two district's temperature: 225-230 ℃, and three district's temperature: 235-250 ℃; Four district's temperature: 240-260 ℃, five district's temperature: 230-250 ℃, six district's temperature: 220-245 ℃; Seven district's temperature: 240-250 ℃, engine speed: 300-350rpm.
With the particle of accomplishing as stated above in 100~130 ℃ convection oven dry 4 hours in advance; And then the particulate material that drying is good carries out the injection molding sample preparation on injector; The injection mold temperature control is at 90 ℃, and the injection moulding temperature is controlled at 230-260 ℃.
The invention has the beneficial effects as follows: the present invention is soaked into thomel through adopting liquid polyacrylonitrile oligopolymer earlier; Through thomel that soak into to handle again after preoxidation; Polyacrylonitrile is adsorbed on carbon fiber surface and forms a large amount of active itrile groups, and these itrile groups and polar resin have extraordinary linkage force, has improved the cementability of thomel and polar resin; Improved the surface polarity of thomel; Strengthened the cohesive force of thomel and resin matrix, the intensity height of gained carbon fibre reinforcement product, good toughness, production technique are simple, can be widely used in carbon fiber reinforced automobile, military project apparatus, aviation and use the high performance structures material.
Embodiment
The present invention provides a kind of carbon fiber reinforced polyester matrix material and preparation method thereof, and the present invention carries out surface treatment with thomel earlier, and specifically comprise: wherein surface treatment of carbon fibers agent is prepared from following component by mass percentage: solvent 0-99%; Polyacrylonitrile 1-100%.
Described solvent is a polar solvent, comprises in water, ethanol, methyl alcohol, the acetone one or more.Described thomel is the thomel of polyacrylonitrile-radical.Described polyacrylonitrile is liquid polyacrylonitrile oligopolymer, and its molecular weight ranges is: 106-10000 dalton.
Carbon fiber surface treatment method, concrete steps comprise:
Step 1: with polyacrylonitrile with stir after solvent mixes by mass percentage;
Step 2: the solvent that thomel is soaked into step 1;
Step 3: will in 50-300 degree centigrade of baking oven, obtain surface processed carbon fiber in preoxidation 0.01-100 hour through thomel that soak into to handle.
Above-mentioned thomel that obtains and polarity vibrin are prepared carbon-fibre composite, are exemplified below:
Embodiment 1
The preparation method of matrix material is following: with polyethyleneterephthalate (PET) mass ratio be: 69.6%; Lubricant (Zinic stearas) mass ratio is: 0.2%; Oxidation inhibitor (phenolic antioxidant four [β-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester) mass ratio is: 0.2%.In high-speed mixer, mixed 4 minutes;
Each component that mixes places twin screw extruder, and through the melting mixing extruding pelletization, thomel 30% adds in the forcing machine with the side feeding manner;
Its processing temperature is district's temperature a: 210-220 ℃, two district's temperature: 225-230 ℃, and three district's temperature: 235-250 ℃; Four district's temperature: 240-260 ℃, five district's temperature: 230-250 ℃, six district's temperature: 220-245 ℃; Seven district's temperature: 240-250 ℃, engine speed: 300-350rpm.
With the particle of accomplishing as stated above in 100~130 ℃ convection oven dry 4 hours in advance; And then the particulate material that drying is good carries out the injection molding sample preparation on injector; The injection mold temperature control is at 90 ℃, and the injection moulding temperature is controlled at 230-260 ℃.
Embodiment 2
The preparation method of matrix material is following: with polyethyleneterephthalate (PET) mass ratio be: 59.6%; Lubricant (Zinic stearas) mass ratio is: 0.1%; Oxidation inhibitor (phenolic antioxidant four [β-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester) mass ratio is: 0.3%.In high-speed mixer, mixed 4 minutes;
Each component that mixes places twin screw extruder, and through the melting mixing extruding pelletization, thomel 40% adds in the forcing machine with the side feeding manner;
Its processing temperature is district's temperature a: 210-220 ℃, two district's temperature: 225-230 ℃, and three district's temperature: 235-250 ℃; Four district's temperature: 240-260 ℃, five district's temperature: 230-250 ℃, six district's temperature: 220-245 ℃; Seven district's temperature: 240-250 ℃, engine speed: 300-350rpm.
With the particle of accomplishing as stated above in 100~130 ℃ convection oven dry 4 hours in advance; And then the particulate material that drying is good carries out the injection molding sample preparation on injector; The injection mold temperature control is at 90 ℃, and the injection moulding temperature is controlled at 230-260 ℃.
Embodiment 3
The preparation method of matrix material is following: with polyethyleneterephthalate (PET) mass ratio be: 79.6%; Lubricant (Zinic stearas) mass ratio is: 0.2%; Oxidation inhibitor (phenolic antioxidant four [β-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester) mass ratio is: 0.2%.In high-speed mixer, mixed 4 minutes;
Each component that mixes places twin screw extruder, and through the melting mixing extruding pelletization, thomel 20% adds in the forcing machine with the side feeding manner;
Its processing temperature is district's temperature a: 210-220 ℃, two district's temperature: 225-230 ℃, and three district's temperature: 235-250 ℃; Four district's temperature: 240-260 ℃, five district's temperature: 230-250 ℃, six district's temperature: 220-245 ℃; Seven district's temperature: 240-250 ℃, engine speed: 300-350rpm.
With the particle of accomplishing as stated above in 100~130 ℃ convection oven dry 4 hours in advance; And then the particulate material that drying is good carries out the injection molding sample preparation on injector; The injection mold temperature control is at 90 ℃, and the injection moulding temperature is controlled at 230-260 ℃.
Embodiment 4
The preparation method of matrix material is following: with polybutylene terephthalate (PBT) mass ratio be: 69.6%; Lubricant (Zinic stearas) mass ratio is: 0.1%; Oxidation inhibitor (phenolic antioxidant four [β-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester) mass ratio is: 0.3%.In high-speed mixer, mixed 4 minutes;
Each component that mixes places twin screw extruder, and through the melting mixing extruding pelletization, thomel 30% adds in the forcing machine with the side feeding manner;
Its processing temperature is district's temperature a: 230-240 ℃, two district's temperature: 235-250 ℃, and three district's temperature: 245-270 ℃; Four district's temperature: 250-280 ℃, five district's temperature: 240-270 ℃, six district's temperature: 230-265 ℃; Seven district's temperature: 250-270 ℃, engine speed: 300-350rpm.
With the particle of accomplishing as stated above in 100~130 ℃ convection oven dry 4 hours in advance; And then the particulate material that drying is good carries out the injection molding sample preparation on injector; The injection mold temperature control is at 90 ℃, and the injection moulding temperature is controlled at 230-260 ℃.
Embodiment 5
The preparation method of matrix material is following: with polyethyleneterephthalate (PET) mass ratio be: 34.8%; Polyethyleneterephthalate (viscosity resin in the injection grade) mass ratio is: 34.8%; Lubricant (Zinic stearas) mass ratio is: 0.2%; Oxidation inhibitor (phenolic antioxidant four [β-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester) mass ratio is: 0.2%.In high-speed mixer, mixed 4 minutes;
Each component that mixes places twin screw extruder, and through the melting mixing extruding pelletization, thomel 30% adds in the forcing machine with the side feeding manner;
Its processing temperature is district's temperature a: 220-230 ℃, two district's temperature: 235-240 ℃, and three district's temperature: 245-260 ℃; Four district's temperature: 250-270 ℃, five district's temperature: 240-260 ℃, six district's temperature: 230-255 ℃; Seven district's temperature: 250-260 ℃, engine speed: 300-350rpm.
With the particle of accomplishing as stated above in 100~130 ℃ convection oven dry 4 hours in advance; And then the particulate material that drying is good carries out the injection molding sample preparation on injector; The injection mold temperature control is at 90 ℃, and the injection moulding temperature is controlled at 230-260 ℃.
Comparative Examples 1
The preparation method of matrix material is following: with polyethyleneterephthalate (PET) mass ratio be: 69.6%; Lubricant (Zinic stearas) mass ratio is: 0.2%; Oxidation inhibitor (phenolic antioxidant four [β-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester) mass ratio is: 0.2%.In high-speed mixer, mixed 4 minutes;
Each component that mixes places twin screw extruder, and through the melting mixing extruding pelletization, not surface treated thomel 30% adds in the forcing machine with the side feeding manner;
Its processing temperature is district's temperature a: 210-220 ℃, two district's temperature: 225-230 ℃, and three district's temperature: 235-250 ℃; Four district's temperature: 240-260 ℃, five district's temperature: 230-250 ℃, six district's temperature: 220-245 ℃; Seven district's temperature: 240-250 ℃, engine speed: 300-350rpm.
Comparative Examples 2
The preparation method of matrix material is following: with polybutylene terephthalate (PBT) mass ratio be: 69.6%; Lubricant (Zinic stearas) mass ratio is: 0.1%; Oxidation inhibitor (phenolic antioxidant four [β-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester) mass ratio is: 0.3%.In high-speed mixer, mixed 4 minutes;
Each component that mixes places twin screw extruder, and through the melting mixing extruding pelletization, not surface treated thomel 30% adds in the forcing machine with the side feeding manner;
Its processing temperature is district's temperature a: 230-240 ℃, two district's temperature: 235-250 ℃, and three district's temperature: 245-270 ℃; Four district's temperature: 250-280 ℃, five district's temperature: 240-270 ℃, six district's temperature: 230-265 ℃; Seven district's temperature: 250-270 ℃, engine speed: 300-350rpm.
With the particle of accomplishing as stated above in 100~130 ℃ convection oven dry 4 hours in advance; And then the particulate material that drying is good carries out the injection molding sample preparation on injector; The injection mold temperature control is at 90 ℃, and the injection moulding temperature is controlled at 230-260 ℃.
The tensile property test is undertaken by ASTM D638 standard, and specimen size is 150mm*12mm*3.5mm, and draw speed is 50mm/min; The bending property test is undertaken by ASTM D790, and specimen size is 80mm*12mm*3.5mm, and draw speed is 2mm/min; Span is 48mm; The socle girder notched Izod impact strength is undertaken by ASTM D256, and specimen size is 55mm*12.6mm*3.5mm, and notch depth is 1/3rd of a sample thickness.
The numerical value of the tensile strength of comprehensive mechanical performance through test gained batten, flexural strength, modulus in flexure, shock strength is passed judgment on.
Embodiment 1-5 and Comparative Examples 1,2 performances are as shown in table 1
Table 1 embodiment and Comparative Examples
Figure BDA0000041876700000071
From the embodiment 1-5 performance of table 1 relatively, along with the increase of carbon fiber content, the intensity of matrix material also constantly increases; Can find out that with the performance comparison of Comparative Examples 2 the carbon fiber reinforced polyester composite material strength of treated dose of processing increases considerably from embodiment 1 and Comparative Examples 1 and embodiment 4.
More than a kind of carbon fiber reinforced polyester matrix material provided by the present invention and preparation method thereof has been carried out detailed introduction; Used concrete example among this paper principle of the present invention and embodiment are set forth, the explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof; Simultaneously, for one of ordinary skill in the art, according to thought of the present invention, the part that on embodiment and range of application, all can change, in sum, this description should not be construed as limitation of the present invention.

Claims (8)

1. carbon fiber reinforced polyester matrix material is characterized in that: it is formed by the quality proportioning and is (%):
Polyester 60-80%
Lubricant 0.1-0.3%;
Oxidation inhibitor 0.1-0.3%;
Thomel 20-40%.
2. carbon fiber reinforced polyester matrix material according to claim 1 is characterized in that said polyester is polybutylene terephthalate or polyethyleneterephthalate one or both mixtures wherein.
3. carbon fiber reinforced polyester matrix material according to claim 1 is characterized in that said lubricant is a Zinic stearas.
4. carbon fiber reinforced polyester matrix material according to claim 1 is characterized in that said oxidation inhibitor is four [β-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester.
5. carbon fiber reinforced polyester matrix material according to claim 1 is characterized in that said thomel is through liquid polyacrylonitrile surface treatment.
6. like the said carbon fiber reinforced polyester matrix material of claim 5, it is characterized in that said thomel preparation method comprises:
Step 1: with stirring after polyacrylonitrile and the solvent;
Step 2: the solvent that thomel is soaked into step 1;
Step 3: will in 50-300 degree centigrade of baking oven, obtain the polyacrylonitrile surface processed carbon fiber in preoxidation 0.01-100 hour through thomel that soak into to handle.
7. a carbon fiber reinforced polyester composite material and preparation method thereof according to claim 1 is characterized in that, comprises step:
A: by mass percentage resin, lubricant, oxidation inhibitor were mixed in high-speed mixer 4 minutes;
B: each component that mixes places twin screw extruder, presses mass ratio thomel is added extruding pelletization in the forcing machine with the side feeding manner, through the melting mixing extruding pelletization;
C: its processing temperature is district's temperature a: 210-220 ℃, two district's temperature: 225-230 ℃, and three district's temperature: 235-250 ℃; Four district's temperature: 240-260 ℃, five district's temperature: 230-250 ℃, six district's temperature: 220-245 ℃; Seven district's temperature: 240-250 ℃, engine speed: 300-350rpm.
8. like the said carbon fiber reinforced polyester composite material and preparation method thereof of claim 7; It is characterized in that; Also comprise: the particle that will accomplish as stated above in 100~130 ℃ convection oven dry 4 hours in advance; And then the particulate material that drying is good carries out the injection molding sample preparation on injector, and the injection mold temperature control is at 90 ℃, and the injection moulding temperature is controlled at 230-260 ℃.
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102161817A (en) * 2011-05-17 2011-08-24 深圳市科聚新材料有限公司 Carbon fibre reinforced polyester composite material and preparation method thereof
CN102719059A (en) * 2012-07-06 2012-10-10 上海日之升新技术发展有限公司 Polyester fiber-reinforced polyester material and preparation method thereof
CN103161073A (en) * 2013-03-26 2013-06-19 金发科技股份有限公司 Emulsion carbon fiber sizing agent and preparation method and application thereof
CN103161072A (en) * 2013-03-26 2013-06-19 金发科技股份有限公司 Sizing agent for emulsion type carbon fibers as well as preparation method and application thereof
CN105694390A (en) * 2016-03-17 2016-06-22 合肥晨煦信息科技有限公司 Carbon fiber composite
CN108177402A (en) * 2018-01-03 2018-06-19 江苏澳盛复合材料科技有限公司 A kind of carbon glass mixing reinforcing material
CN110607693A (en) * 2019-09-25 2019-12-24 安徽旭升新材料有限公司 Method for modifying carbon fiber in carbon fiber PA66 thermoplastic composite material
CN111098466A (en) * 2019-12-26 2020-05-05 苏州市爱司特塑胶五金有限公司 Injection molding process of carbon fiber polypropylene composite material

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CN101633774A (en) * 2009-08-28 2010-01-27 金发科技股份有限公司 PBT molding composite and preparation method thereof

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102161817A (en) * 2011-05-17 2011-08-24 深圳市科聚新材料有限公司 Carbon fibre reinforced polyester composite material and preparation method thereof
CN102161817B (en) * 2011-05-17 2013-12-04 深圳市科聚新材料有限公司 Carbon fibre reinforced polyester composite material and preparation method thereof
CN102719059A (en) * 2012-07-06 2012-10-10 上海日之升新技术发展有限公司 Polyester fiber-reinforced polyester material and preparation method thereof
CN102719059B (en) * 2012-07-06 2015-02-25 上海日之升新技术发展有限公司 Polyester fiber-reinforced polyester material and preparation method thereof
CN103161073A (en) * 2013-03-26 2013-06-19 金发科技股份有限公司 Emulsion carbon fiber sizing agent and preparation method and application thereof
CN103161072A (en) * 2013-03-26 2013-06-19 金发科技股份有限公司 Sizing agent for emulsion type carbon fibers as well as preparation method and application thereof
CN103161072B (en) * 2013-03-26 2015-06-03 金发科技股份有限公司 Sizing agent for emulsion type carbon fibers as well as preparation method and application thereof
CN103161073B (en) * 2013-03-26 2015-06-10 金发科技股份有限公司 Emulsion carbon fiber sizing agent and preparation method and application thereof
CN105694390A (en) * 2016-03-17 2016-06-22 合肥晨煦信息科技有限公司 Carbon fiber composite
CN108177402A (en) * 2018-01-03 2018-06-19 江苏澳盛复合材料科技有限公司 A kind of carbon glass mixing reinforcing material
CN110607693A (en) * 2019-09-25 2019-12-24 安徽旭升新材料有限公司 Method for modifying carbon fiber in carbon fiber PA66 thermoplastic composite material
CN111098466A (en) * 2019-12-26 2020-05-05 苏州市爱司特塑胶五金有限公司 Injection molding process of carbon fiber polypropylene composite material

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